Abstract
Analogous to surface premelting, we show that a crystal surface can undergo a pre-solid–solid transition. This means that it develops a thin polymorphic crystalline layer before reaching the solid–solid transition temperature if two crystals can form a low-energy coherent interface. We confirm this in simulations and colloid experiments at single-particle resolution. The power-law increase of surface layer thickness is analogous to premelting. Different kinetics and reversibilities of surface-crystal growth are observed in various systems. Surface crystals exist not only under thermal equilibrium but also during melting, crystallization and grain coarsening. Furthermore, the premelting and pre-solid–solid transition can coexist, resulting in double surface wetting layers. We hypothesize that such surface phenomena also exist in some atomic and molecular crystals, and this could provide a mechanism to tune the properties of the materials.
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Acknowledgements
We thank D. Frenkel, J. Dobnikar, W. Li, Q. Zhang and K. Qiao for useful discussions, X. Xu for part of the computational facility and Y. Zhang and Y. Wang for the NIPA colloid. This work was supported by RGC-CRF grant no. C6016-20G, Guangdong Basic and Applied Basic Research Foundation grant no. 2020B1515120067 and Chinese National Science Foundation through grant no. 12104495.
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Y.H. and B.L. proposed the existence of the surface-crystal phenomena. Y.H., B.L. and X.W. conceived and designed the research. X.W. carried out the simulations. B.L. and M.L. conducted the experiments with PMMA and NIPA colloids, respectively. B.L., X.W. and M.L. analysed the data, with help from Y.H. X.W., Y.H. and B.L. wrote the paper. Y.H. supervised and supported the work. All authors discussed the results.
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Supplementary Results
Supplementary Video 1
The initial formation of the surface 4□ PMMA colloidal crystal. The 4□ layer covers the 4△ surface, corresponding to Fig. 2a,b.
Supplementary Video 2
The growth of the surface 4□ PMMA colloidal crystal. 4△ → 4□, corresponding to Fig. 2c–e.
Supplementary Video 3
The bulk 4△ NIPA colloidal crystal transforms to a surface 4□ crystal layer by layer. The temperature is changed from 33.5 °C to 34 °C at t = 0. Particles involving the transformation are coloured in red for △ lattice and green for □ lattice in the left panel. 50 × real time.
Supplementary Video 4
Shrinkage of the 4□ crystal by increasing the temperature. The surface 4□ crystal transforms back to bulk 4△ PMMA colloidal crystal when the temperature increases from 25.5 °C to 26.0 °C, corresponding to Supplementary Fig. 4.
Supplementary Video 5
The four layers in the z direction exhibit the same behaviours during the pre-s–s transition (simulation). 12-6 LJ particles at t = 2.0 × 105 after the temperature is changed from T = 0.485 to T = 0.489 at t = 0, corresponding to Fig. 2h–k. Particles in the xz, yz and xy plane are shown at 60%, 60% and 90% of their true size to be clearly displayed.
Supplementary Video 6
The four layers in the z direction exhibit the same behaviours during the pre-s–s transition (experiment). The NIPA sample is scanned along the z direction by changing the focal plane at 30 °C. The moving objective slightly perturbs the colloid.
Supplementary Video 8
The melting process of a bulk △ crystal involves a transient surface 4□ crystal. The temperature is changed from 33 °C to 34 °C at t = 0 in the NIPA colloid, corresponding to Fig. 4a–c.
Supplementary Video 9
The crystallization of a bulk △ crystal involves a transient surface 4□ crystal. The temperature is changed from 33 °C to 27 °C in the PMMA colloid, corresponding to Fig. 4d–f. 1.57 × real time.
Supplementary Video 10
Double layers on the surface of a 4△ NIPA colloidal crystal. The liquid and 4□ surface wetting layers are stable after more than 150 min at 33 °C, corresponding to Fig. 5a.
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Wang, X., Li, B., Li, M. et al. Polymorphic crystalline wetting layers on crystal surfaces. Nat. Phys. 19, 700–705 (2023). https://doi.org/10.1038/s41567-022-01923-2
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DOI: https://doi.org/10.1038/s41567-022-01923-2